Cotton treated with a cation active amine



Patented Sept. 13, 1949 COTTON TREATED WITH A GATION ACTIVE AMINE PaulHenry Schlosser and Kenneth Russell Gray,

Shelton, Wash., asslgnors to Bayonler Incorporated, Shelton, Wash., acorporation of Delaware N; Drawing. Application April 12, 1944, SerialNo. 530,740

This invention relates to the production of cellulosic products and hasfor its object the provision of certain improvements in the productionof cellulosic products from cotton, and particularly cotton linters. Theinvention is of special advantage in the production of regeneratedcellulose products, and particularly by the viscose process, fromcotton. A further object of the intextile operation to form it intothreads or fabric;

and in the appended claims the term cotton in the raw state is used todesignate raw cotton or raw cotton which has been subjected to chemicaltreatment to purify and bleach it, as hereinafter referred to, but whichhas not been subjected to any textile operation to form it intothreadsor fabric. The invention aims to incorporate in such cotton, orits derivatives, one or more added compounds of the invention to improveone or more of the steps in the formation of the cellulosic products.

Chemical cotton in sheet form is customarily subjected to comminution orshredding as one of the preliminary steps in its processing. In theproduction of viscose, for example, the sheets formed of cotton lintersare usually steeped in a caustic soda solution to form alkali celluloseand a the alkali cellulose, after pressing and while still in sheetform, is shredded to prepare the cotton fibers for the xanthatingreaction with carbon bisulfide. The resulting sodium cellulose xanthateis dissolved in dilute caustic soda to form the solution commonly knownas viscose which, opaciiied if desired, is filtered and spun intofilaments.

We have discovered that the incorporation in cotton, advantageously incotton linters, of certain compounds in minute quantities, imparts tothe cellulose, properties that make it more amenable to variousprocessing steps in the production of rayon by the viscose process,resulting in increased efllciency and a decrease in the cost of theoperation. The invention accordingly involves the incorporation in thecotton of a small 5 Claims. (01.106-185) the utilization of the cottonso treated for the production of viscose rayon. The invention providesas an article of manufacture an improved product comprising cotton,especially cotton linters, having one or more of said compoundsincorporated therein.

In practices proposed heretofore, cation-active compounds as strongbases or their salts including quaternary ammonium, sulphonium,phosphonium and arsonium salts have been used in the spin bath to reduceincrustations in the spinneret orifices. When added to the viscose, suchcompounds also reduce incrustations in spinneret orifices, though ingeneral considerably larger concentrations are required to be presentand such additions will frequently cause certain disadvantages as willbe presently set forth.

We have made the discovery that important new advantages accrue if thereis caused to be a present in the viscose, in a manner, as .will bespecified, compounds which have only a weakly cation-active behaviorwhile in the viscose, but which becomes strongly cation-active at thepoint of spinning. For such purposes, we find that cation-active aminocompounds are eminently suitable.

The cation-active amino compounds or agents of the invention when usedin the manner of the invention yield all of the advantages hithertoobtainable only by use of larger amounts of quaternary ammoniumcompounds. In addition, the agents of our invention, yield important newadvantages and are free or largely free from the disadvantagesaccompanying the use in viscose of highly ionized cation-activematerials such as cation-active quaternary ammonium compounds.

Cation-active amino compounds in alkaline solution derive theirattraction for water from one or more weakly hydrophilic aminogroupsrather than from strongly hydrophilic groups as in the case ofquaternary ammonium com-' pounds. Accordingly, in many casescationactive amino compounds will not be clearly soluble in caustic sodasolutions, but will disperse rather than dissolve. It would be thoughtthat it would be disadvantageous to use materials that would disperserather than dissolve in viscose. Actually, if such materials which tendto disperse rather than completely dissolve are added directly to theviscose, they will be only partially effective due to incompleteness ofthe dispersion. Also, with the more difllculty dispersible cationactiveamino compounds, when added directly to the viscose the incompletenessof dispersion may quantity ofa cation-active amino compound and be suchthat considerable of the agent may be 3 removed during the customaryviscose filtration operations with the result that the filtering media.may become rapidly clogged. requiring fl'G-e quent replacement. Thesedifil culties are not encountered when the agents are added in themanner of the invention-by impregnating the cellu-- lose base material,preferably cotton linters, with the agents prior. to use in the viscoseprocess. The impregnation is preferably carried out by use of an aqueoussolution or dispersion of the agent, best in the form of a soluble saltsuch as the acetate. When the cellulosic base material is treated withthe agent in this manner, the agents of the invention become dispersedin the viscose in a very fine state so that they are very effective inaccomplishing the purposes of the invention.

All purified cellulose base materials commonly used for the preparationof viscose rayon contain varying amounts of anion-active materials or ofmaterials which will give rise to anionactive materials when in contactwith caustic soda during the various steps of the viscose process. Suchanion-active materials will'be predominantly fatty and resin acid soaps.Cotton linters will generally contain appreciably smaller amounts ofsuch soap-forming materials than will most purified wood pulps. Cottonlinters, however, when used for viscose rayon, are frequently blendedwith purified wood pulps in order to improve spinning and otherprocessing conditions. In such cases, the resulting viscose solutionswill contain appreciable amounts of anion-active materials and maycontain additional amounts if the wood pulp has been treated inaccordance with United States Patent 2,331,935.

Also, when cotton linters are used in the viscose process, relativelylarge amounts of anion-active materials are frequently added. to theviscose or the viscose-forming materials to reduce milkiness in therayon or to otherwise improve the spinning operations. Such additions ofanion-active materials are made frequently in the cases where the cottonlinters are not mixed with purified wood pulp prior to processing. Thus,whether the cotton is processed alone or in admixture with wood pulp,the resulting solutions will, in most cases, contain appreciable amountsof anion-active materials.

Cation-active quaternary ammonium compounds, while very useful forsuppressing formation of incrustations in spinneret holes, nevertheless,when introduced into the viscose rather than the spin bath possess aconsiderable disadvantage in that they are not very compatible withanion-active materials. If cation-active quaternary ammonium compoundsare introduced into viscose in which there happens to be present anapproximately equivalent amount of anion-active materials, an actualprecipitation of materials may occur in the viscose or at the very leastthe viscose may become very turbid. Such precipitated material is likelyto plug the filters and cause spinning troubles.

Even when the relative proportions of cationactive quaternary ammoniumcompounds and anion-active materials are such that actual precipitationdoes not occur, troubles may still be encountered through simultaneoususe of the two types of materials. Such troubles are particularlyencountered when the anion-active materials are present in sufficientquantity to predominate over the quaternary ammonium compounds and thisviscose is opacifled by oleaginous materials such as mineral oil, orpine oil or by Gil means of opaeifying agents containing oleaginousmaterials. In general, where a cation-active quaternary ammoniumcompound is added in amounts insufficient to predominate overanionactive materials present, the effect is to make the emulsion poorerthan if only the anion-active materials had been present. In such casesthe effect of the cation-active quaternary ammonium compound will be tocause a greater lack of uniformity of the emulsion in regard to particlesize and in particularto bring about the presence of numerous globulesconsiderably larger than theaverage particle size. Such large globuleseven when relatively few in quantity are very harmful in that they causeirregularities in the viscose filaments and resulting places ofweakness. In some cases when cation-active quaternary ammonium compoundsare used in the presence of predominating amounts of anion-activematerials the interference with the emulsiilcation or with the stabilityof the emulsions. may be such that large visible drops or pools of oilwill separate and float on top of the emulsion. One way ofovercomingsuch difllculties might be to use very large amounts of thecation-active quaternary ammonium compounds so that they wouldsubstantially predominate over the anion-active materials present. Thiswould be very expensive since cation-active quaternary ammoniumcompounds are much more expensive than commonly used anion-activematerials. However, the additions of very high amounts of cation-activequaternary ammonium compounds are accompanied by serious disadvantagesother than as regards the matter of expense. In making high grade rayonit is essential that all foreign materials or impurities be eliminatedand therefo' the adding 01' very large amounts of cation-act quaternaryammonium compoundsis proceeding directly against the requirement of theelimination from the cellulosic base material of all materials otherthan the cellulose itself. Again, the use of very large amounts ofcation-active quaternary ammonium compounds will tend to cause certaindisadvantages which include (a) excessive roaming when mixing theviscoses; (b) difilculties in subsequently deaerating the viscose,

and (c) difilculties in spinning due to the very low surface tension ofthe viscose.

The agents of our invention, however, are much more compatible withanion-active materials than are cation-active quaternary ammoniumcompounds. Their use in viscose is therefore not accompanied by thedisadvantages of the cationactive quaternary ammonium compounds.

The agents of our invention moreover are more efi'ective in that theycan be used in much smaller concentrations, even in the presence ofanionactive materials. The agents of our invention also produce newadvantages. Not only is the proces of our invention inexpensive tooperate in that only very small quantities of the agents are requiredbut, moreover, the agents themselves are in general eonsiderabbr less ep nsive than the previously used types of cation-active compounds. Thecationactive amino compounds in general may be very inexpensivelyproduced from the natural fats and other readily available rawmaterials.

Not only are the cation-active agents of our invention compatible withthe anion-active compounds that will be commonly present in viscosesolutions (either naturally or by addition) but the agents of ourinvention actually improve the emulsifying action of the anion-activecompounds. This improvement relates particularly to the imparting ofstability against creaming of emulsions prepared using oleaginousopacifying agents and viscose containing anion-active emulsifyingagents; e. g., fatty and resin acid soaps.

Many anion-active emulsifying sents while not yielding emulsions of oilin viscose having as fine average particle size and uniformity as thosespecified in United States Patent No. 2,373,712, nevertheless arerelativeb' inexpensive and yield emulsions that will be satisfactory formany purposes with reference to particle size and stability in regard tomaintaining particle size. Such emulsions, however, have a tendency tocream partially or for part of the oil to separate out as a scum duringthe various viscose processing steps or during the aging period. We findthat the addition of very small amounts of the cationactive agents ofour invention either eliminates or greatly diminishes the tendency ofthe emulsions to cream. While all the agents of our discovery areeffective in this regard, the best results are obtained by the moredispersible cation-active amino compounds, usually compounds containinga plurality of amino groups. Thus octadecylamine (acetate) has anextremely small anticreaming effect. Dodecylamine or the mixture ofnormal primary amines from coconut fatty acids have a greater but stillsmall antl-creaming action. Materials, however, such as mixtures of themonoand diamides of coconut fatty acids and diethylene triamine, whichare very readily dispersible, exert a very powerful emulsionanticreaming effect even when added in very small quantities.

When even those cation-active amino compounds having the greatestanti-oreaming action are added directly to the viscose either prior orduring emulsification, very little reduction in oreaming is obtained.when, however, these. agents are added to the alkali cellulose prior tothe completion of shredding or preferably to the cellulose base materialprior to use in the viscose process, complete or substantial reductionin creaming is obtained.

Especially good emulsification results are obtained when there is addedto the cotton linters in addition to the small amounts of cation-activeamino compounds, also small amounts of a mixed ether containing apolyethylene oxide radical and an aliphatic hydrocarbon radicalcontaining more than '7 carbon atoms. The very best results occur whenthe said mixed ether contains a polyethylene oxide radical of 9 toethenoxy residues and a normal aliphatic hydrocarbon radical having from12 to 18 carbon atoms. Such emulsions not only are characterized by ahigh degree of non-creaming stability but also are characterized by anextremely fine and uniform particle size with almost complete absence ofsubstantially larger globules. The emulsions are also very stable inregard to maintaining the fineness and uniformity of the particle sizeIn addition to the advantages already outlined, the use of the agents ofour invention also gives a very great general improvement in spinningperformance. By this improvement we refer to benefits apart from thatbrought about by obtaining less incrustation of spinneret holes, Thesegeneral improvements include especially improvements in coagulation ofthe cellulose resulting in less sticking of the freshly formed yarn tothe spinning guides and fewer broken filaments. This is of the utmostpractical importance 6 since it enables substantially reducing theproportion of of! grade yarn produced.

Amino groups are of three types: Primary, secondary and tertiary. Eachof these types may exist in five different forms to a different degree(in some cases completely and in others to only a small degree):

1. Free amino group-anhydrous.

2. Free amino group-hydrated and not ionized. 3. Free aminogroup-hydrated and ionllcd.

4. Amino group in form of salts with acids-non- 5'. 'Amino group in formof salts with acids-ion- The three types in their different forms may beshown as follows:

In the table above the free bonds shown represent carbon-nitrogenlinkages, while the symbol "X representsthe anion of an acid forming asalt with the free amino group.

Generally in the presence of water, an amino group in the form of a salt(substituted ammonium salt) will be largely in the ionized form.

' In the presence of water (except in very dilute solutions), compoundscontaining one free amino group, however, will exist largely in thenonionized form's, hydrated and anhydrous. Obviously, with compoundscontaining a multiplicity of free amino groups in the presence of wateras in viscose solutions, there will be a greater proportion of moleculeshaving at least one amino group in the hydrated, ionized form. However,even in such cases, the percentage of ionized molecules will beextremely small so that the compounds will be only extremely weaklyionized; i. e.,

only very weakly basic and, hence, though surface-active, only weaklycation-active.

As used generically in this application, the term amino compoun refersto a compound having at least one of any of the three types of aminogroups shown in the table in any one, or in an equilibrium mixture ofmore than one, of the five forms shown.

Surface-active compounds are compounds containing one or more lipophilic(oil or fat attracting, water repulsing) groups together with ahydrophllic group or a plurality of hydrophilic groups. Further, thelipophilic group or groups must be of sufilcient magnitude to impart toa portion of the molecule a substantial repulsive action towards water.The hydrophilic group or plurality of hydrophilic groups must possess a'sufilcient hydrophillc character so that the molecule is water-solubleor at least soluble to the ex vided form in water.

7 tent that it is readily dispersible in annely di- The surface-activeproperty of molecules thus arises as the result of their containing atleast one hydrophilic (water attracting) group and at least onelipophilic (fat or oil attracting and hence water 'repulsing) group. Byvirtue of the compounds containing a hydrophilic group, they are atleast to a certain extent soluble in water. However, by virtue of theircontaining a lipophilic group, they tend to be repulsed by the water.Thus they tend to concentrate largely on the surface of the water orinterface layer where they can take up a compromise position with thehydrophilic group resting in the water and the lipophilic group stickingout of the water.

The compounds of the invention are such surface-activelipophilic-hydrophilic combinations in which the hydrophilic effect isprovided either wholly or in part through the presence of an amino groupor a plurality of amino groups. That the compounds are cation"-active isdue to the fact that they will ionize either largely through the form oftheir salts with acids 'or to a small extent through the form of ahydrated free amino group.

Where the compounds contain a plurality of amino groups, these arepreferably connected by short links-for example, by ethylene groups orby segments of a ring, though longer connecting links are not ruled out.

Many of the compounds of the cation-active amino class while soluble anddefinitely cationactive in the form of their salts with acids are.nevertheless, neithersoluble nor readily dispersible in strong causticsoda solutions. Such materials, when added as a solution in salt form,to a, solution containing excess alkali, separate outalmost completelyin the form of oils or solid precipitates. Due to the lack of solubilityor dispersibility in an alkaline medium, such compounds might possiblynot normally be considered to be efl'ective in alkaline solutions. When,however, they are added to the cotton in the from of soluble salts, theysubsequently disperse in the viscose and are effective in the process ofthe invention.

While the compounds of the invention are not necessarily dispersible orsoluble in the free base form, the free bases must, nevertheless, besubstantially stable in solutions of alkali metal hydroxide.- r

Where the compounds are employed as salts, the salts of any acid whoseanion would normally be innocuous in small concentrations to the viscoseprocess may be used. Such innocuous anions include acetate, chloride,sulphate, etc. We believe in many cases best results will be'obtainedwith the acetates. These salts are less acidic than similar salts ofmineral acids and are thus preferred when treating the cotton linters.Also with those amino compounds of the invention that tend to formdiillcultly soluble salts, the acetates are frequently more soluble ordispersible than the salts of mineral acids.

In the compounds of the ention the lipophilic group (or each of thelipophilic groups) has substantially a hydrocarbon character but is notlimited to hyrocarbon radicals.

Among the important lipophilic groups are the radicals R,

, The aliphatic hydrocarbon radicals represented by R include straightchain, branched chain, saturatedand unsaturated radicals. Other groupssuch as cyclic hydrocarbon groups or groups containing a smallproportion of other elements than carbon and hydrogen are, however,not.excluded.

A lipophilic aliphatic hydrocarbon radical (It) may be connecteddirectly to the amino group (or to one of the plurality of aminogroups). The lipophilic groups I 0 r -mmand R-O are, however. alwaysconnected to the nitrogen through stable intermediary linkspreferably,though not restricted to, short alkylene groups such as the ethylenegroup (-OHsCHs-l. In regard to the use of the lipophilic groups R.

R("!NH and R-O- to induce surface activity; suitablegroups will includethose having at least '1 carbon atoms. There is a practical upper limitfor these or any other type of lipophilic surface-active inducingradical in that the compounds must be soluble or at least dispersible inwater in the form of salts, if not also as the free base. In thepreferred cases the group R,

l" lit-NH- or R-O-- will have from 7 to 18 carbon atoms. Especially goodresults have been obtained from compounds in which the radicals R,

(H) RC-NH- or R-O- had 12 carbon atoms or were prepared from a vegetableoil, such as coconut oil, predominating in lauric acid so that theresulting radicals were mixtures having predominately 12 carbon atoms.

Among the types and individual examples of.

cation-active amino compounds which may be used are the following:

1. Arxrr. Axmss a. Primary ulkvl amines Primary amines, saturated andunsaturated, straight chain and branched chain with from '7 to 18 carbonatoms are eifective. In view of the fact that the free bases are notreadily dispersible in water by normal procedures and, in view of thefact that the lower free bases are somewhat volatile, these compoundsare most practically applied to the cotton as solutions of water-solublesalts, in most cases preferably as the acetates. Some members can,however, be fairly readily dispersed in water by using specialprocedures, as, for example, by dispersing the alkyl amine in thepresence of a small amount of a soluble salt of the amine.

Among the members of thisseries that we have successfully used are thefollowing:

Heptyl amine, octyl amine, (Z-ethyl) hexylamine-l decylamine, laurylamine, tetradecylamine, hexadecyl amine, oleylamine, octadecylamine. Wehave found the most eifective and practical compound to apply to belauryl amine. Actually the technical mixture of primary amines derivedfrom coconut oil and predominating in lauryl amine works verywell-slightly better than and R-O- where R is a higher aliphatichydrothe pure compound.

The higher members. e. g., octadecylaniine, form salts that are onlyslightly water-soluble,

and whlle giving the advantages of the inven-' tion in part, are moredifllcult to apply in a practical manner.

b. Secondary and may alkyl amines The members of these series will allcontain at least 7 carbon atoms. In all cases the upper limit of carbonatoms will be such that the compounds will formsalts that areappreciably water-soluble. The most preferred types will contain onelong chain while the other chain or chains will be very short,preferably (though not restricted to) methyl or ethyl groups. Examplesare methyl lauryl amine, dimethyl lauryl amine.

These compounds are likewise best applied in the form of water-solublesalts.

2. Anm Auuncmunms (ALKYL Hvnaoxnnxvmmrs) While compounds of this typemay be readily applied in the form ofsoluble salts, many compounds ofthis type are suillciently dispersible in water in free base form to beused as such.

Examples of compounds successfully used include lauryl amino-ethanol(lauryl hydroxyethyl amine), condensation products of lauryl amineandglycerine chlorohydrin, N-bis (Z-ethyl hexyl) amino ethanol.

3. Arm Ernsns or Amnoumrs (Anxrr.

Erans or Hvnnoxranmnmxs) We have used the lauryl ether of ethanolamine(in salt form), the monolauryl ether of triethanolamine (in salt form).

4. Arm Crctoamrvr.

Compounds of this type are best applied in the form of water-solublesalts. Examples are lauryl piperidine, lauryl methyl cyclohexylamine.

5.AmnoAimvzs a. Monoamides of hydroryethyl polyethylene polyaminesCompounds of this type may be applied in the form of water-soluble saltsbut many are sumciently water-dispersible or soluble to be applied infree base form. Suitable hydroxyethyl polyethylene polyamines for use inpreparing the compounds include hydroxyethyl ethylene diamine andhydroxyethyl triethylene tetramine. The preferred amido aminecompoundsof this type are condensation products which are predominantlymonoamides of lrvdroxyethyl ethylene diamine and fatty acids having fromI to 18 carbon atoms.

Examples of compounds successfully used are the monamides ofhydroxyethylethylene diamine and oleic, stearic, and mixed coconut fatty acids (thelatter predominating in lauric acid). The compound derived from acoconut fatty acids is very effective.

b. Partially acylated polyethylene polyamines Polyethylene polyaminesthat we have successfully used in preparing compounds of this typeinclude diethylene triamine, triethylene tetramine and tetraethylenepentamine. The preferred products are polyethylene polyamines partiallyacylated with a fatty acid of from 7 to 18 carbon atoms.

Practically, it is not feasible to prepare a substantially puremonoamide from these polyamines 1o containing 2 primary amino groups,since a substantial amount of diamide will always tend to form inaddition to much smaller amounts of more completely acylated products.We prefer, however, to have the monamide predominate or at least be ashigh as practically possible in any mixture of the two. in order thatthe material will be more water-soluble or dispersible and moreeflective. This will be especially true when the prodnets are formedfrom the lower members of the polyamines. An increase in the proportionof monoamide can be accomplished in their preparation by using an excessof the polyamine over the fatiw acid, or even better'by using an excessof polyamine together with the ethyl or methyl esters of the fattyacids. In either case the excess amine may be substantially removed byvacuum distillation at the end of the reaction.

Examples of products of this type which we have successfully used in thepractice of our invention include products having as the predominatingcompounds the following: Mixtures of the mono and diamides oftetraethylene pentamine and the tions of soluble salts (acetatespreferred) but in' many cases are sufllciently dispersible in free baseform to be applied to the cotton in that condition. Since the productsare not pure compounds, in certain cases (as with hydrochlorides ofcertain products from diethylene triamine) solutions-of the salts willcontain in dispersed form a certain amount of undissolved matter. This,however, does not substantially harm the effectiveness of the productsin the viscose process. 1

Having regard to both the effectiveness of the agents and the practicaleconomics of their preparation, products which are predominantly amixture of the mono and diamides of diethylene triamine and fatty acidsfrom coconut oil, or other vegetable oil, predominating in lauric acidare very effective. Using coconut'fatty acids with a mean molecularweight of 212, a monoamide of diethylene triamine would theoreticallyhave a nitrogen content of about 14.15%, while a diamide would have anitrogen content of about 8.55%. Among the products we have prepared andsuccessfully used, and which are predominantly mixtures of mono anddiamides, are products having the following nitrogen contentsi 8.90%,9.08%. 9.19%, 10.22%, 10.69%, 11.20%, 11.33%, 11.40%, 11.65%, 12.11%,and 12.97%. 'We most usually, however, employ products having nitrogencontents of around 11.2-11.'l% (on an anhydrous basis).

0. Monoamides of derivatives of ethylene dtamine Compounds of this typeare best applied as solutions of soluble salts. An example of a compoundsuccessfully used is the oleic acid amide of unsymmetrical diethylethylene diamine.

In addition to the amido amines described aboveunder (a), (b) and (c)analogous amidines in Compounds of this type are bestapplied in the formof soluble salts. In the preferred cases they will have substituted inthe ring an alkyl chain (saturated or unsaturated) of from 7 to 18carbon Compounds successfully used include z-undecyl imidazoline,z-heptadecyl-ll-acetamidoethyl imidazoline.

'l. Arxxr. Gmmrnnns m Bropsmnms Suitable compounds of this type includegnanidine and biguanidine monalky'lated with an alkyl group of from I to18 carbon'atoms. A preferred compound is lauryl guanidine. .Thesecompounds are best applied in the form of soluble salts.

A preferred form of the. invention contemplates incorporating in cottonlinters a cation-active amino compound of the amido amine type.Cation-active amido amines are readily available and may in general beproduced far more inexpensively than other types of cation-activematcrials. This is because their preparation merely involves heatingcommon fatty acids or fats with low molecular weight'polyamines wherebythe carboxyl group is blocked by amidation but whereby free amino groupsremain. Such compounds, however, are completely hydrolyzed by prolongedtreatment with hot mineral acids. It would thus not be practical to addsuch compounds to a circulatingspin bath to improve spinning. The largevolume of 'the spin bath would necessitate the use of a large amount ofthe amido amine, most of which would become hydrolyzed before coming incontact with the spinnerets.

On the other hand, if such materials were added directly to the viscosethere would in most cases be the problem of obtaining satisfactorydistribution. Cation-active amido amines are most commonly provided inthe form of soluble salts (such as acetates or sulphates). Since thereare salts of very weak bases they cannot exist in alkaline solution. asfor example, in viscose solution. When added directly to viscose, eitheras a dispersion of the free base or as a solution of a soluble salt,such compounds generally either disperse incompletely or partiallyprecipitate. When, however, these compounds are added in the manner ofthe invention to cotton linters before processing into viscose (usingeither a solution of a soluble salt or a dispersion of the free base),none of these disadvantages ensue. Not only is a very completedistribution in the viscose obtained but the compounds only come incontact with the hot acid at the very moment of spinning with the resultthat no measurable amount of the compound is destroyed before it canbecome effective in improving spinning. Not only does the method of ourinvention thus permit the use of relatively inexpensive materials butthese compounds also may be used in smaller amounts since they are moreeffective in improving spinning than compounds previously employed, suchas cation-active quaternary ammonium compounds.

In accordance with our invention, we may mix two or more of theaforementioned compounds to ether to obtain effects not' attainable witha single compound under similar conditions of treatment. For example, wemay use a mixture comprising a cation-active amino compound, cs-

pecially a cation-active amido amine and a mixed ether having attachedto the' ether oxygen a P lyethylene oxide radical and an aliphatichydrocarbon radical having from 7 to 18 carbon atoms. Such mixtures areespecially efficacious in the method of our invention in improvingspinning, enabling the production of yarn of superior quality and alsoin enabling the production of emulsions of oils in viscose characterizedby extreme fineness, uniformity and stability.

- Our invention also contemplates the manufacture of cotton linterscontaining a cation-active amino compound. especially one containing aplurality of nitrogen atoms (as, for example, an amide amine fromdiethylene triamine and coconut fatty acids) to ether with a smallamount of anion-active material or anion-active forming materialespecially fatty or resin acid soaps or of materials capable of formingsuch materials in the presence of caustic soda. The cotton linters mayor may not contain in addition a small amount of a mixed ether of thetypes described above.

A practical and economical manner of securing the desired presence of acompound of our invention during the step of spinning the viscose andduring the step of opacifying the viacose if an opacifying step isemployed is to incorporate the' compound in the cotton usin either asolution, dispersion or emulsion of the salt or free base. dependingupon the compound. Chemical cotton is subjected to a purification andbleaching treatment. The purified and bleached cotton in slush form isthen formed into sheets on a paper machine of conventional design. The

sheet is passed over drying rolls and then cut into sheets of thedesired size.

The compounds may be incorporated either in the loose cotton or in thesheets at any suitable stage, as by spraying the cotton with an aqueoussolution or dispersion of the compound, or by immersing in a solution ordispersion. In any case, there is produced a cotton product having thecompound incorporated therein. When the compound is incorporated in thecotton, as by the manufacture thereof, the cotton comes to the rayonmanufacturer in a form calculated to se cure the full advantages of theinvention in the preparation and processing of the cotton into rayon bythe viscose process.

The amount of the cation-active amino com pound used in the practice ofthe invention is relatively small, ranging from 0.01 to 0.20%, andpreferably from 0.02 to 0.10% by weight on the bone dry weight of thecotton used. So far as the objectives of the invention are concerned,there is little, if any, improvement by increasing the amount of thecompound above 0.20% and such higher amounts frequently give rise tocertain disadvantages. These disadvantages include the causing ofexcessive softness in the sheet, resulting in mechanical dimculties insteeping, dimculties in the dissolving due to excessive foaming in theviscose solution. Also, there may be considerable difliculty inobtaining a completely deaerated viscose which is necessary forsatisfactory spinning. Higher concentrations of the compound may alsounduly lower the surface tension of the viscose. thus changing thecoagulating conditions so that the viscose cannot be satisfactorily spunby standard methods, causing the filaments to break and the thread tostick to the godet wheels or, thread guides.

Where the said mixed ethers are also added these may be added in amountsup to 0.20% but in most cases for best results will be added in therange of 0.02-0.05%. An example of a very emcacious combination would beabout 0.05% of a mixture of a'mido amines from coconut fatty acids anddiethylene triamine together with about 0.03% of a condensation productfrom a higher aliphatic alcohol of from 12-18 carbon atoms (eitherstraight or branched chain), and about -18 moles of ethylene oxide.

While it is our preferred practice to incorporate the compound in thecotton, the presence of the compound during the processing steps ofspinningv and emulsiflcation may be secured in any other appropriatemanner. However, we believe it will generally be found more advantageousto incorporate the compounds in the cotton, both as a matter ofconvenience and economy in preparing and processing the viscose. andbecause a very uniform distribution of the compounds throughout theviscose is easily attained. similar advantages result by incorporatingthe compound, especially the more dispersible compounds, in the alkalicellulose. The incorporation of the compound in the cotton or in thealkali cellulose is particularly important in regard to importinganti-creaming p p rties, especially if the viscose is to be subsequentlyopaciiied.

We claim:

1. As a new article oi manufacture, a cellulosic product consisting ofcotton in the raw state as a raw material for conversion into rayonhaving incorporated therein from 0.01% to 0.2% by weight, based on thebone dry weight of the cotton. of an added cation-active amino compoundselected from the group consisting of an alkyl amine having from 7 to 18carbon atoms, an alkyl alkanolamine having at least one alkyl radicalhaving from 8 to 14'carbon atoms and having from 14 to 18 total carbonatoms, a lauryl ether of an alkanolamine, lauryl piperidine, laurylmethyl cyclohexylamine, an acylated polyethylene polyamine in which theacyl radical has from 7 to 18 carbon atoms, an acylated hydroxyethylpolyethylenepolyamine in which the acyl radical has from 7 to 18 carbonatoms, an alkyl imidazoline having an alkyl radical having from 7 to 18carbon atoms and an alkyl guanidine having an alkyl radical having from7 to 18 carbon atoms.

2. As a new article of manufacture. a cellulosic product consisting ofcotton in the raw state as a raw material for conversion into rayonhaving incorporated therein from 0.01% to 0.2% by weight, based on thebone dry weight of the cotton, of an added cation-active amino compoundselected from the group consisting of an alkyl amine having from 7 to 18carbon atoms, an alkyl alkanolamine having at least one alkyl radicalhaving from 8 to 14 carbon atoms and havin from 14 to 18 total carbonatoms, a lauryl ether of an alkanolamine. lauryl piperidine, laurylmethyl cyclohexylamine, an acylated polyethylene polyamine in which theacyl radical has from 7 to 18 carbon atoms, an acylated hydroxy ethylpolyethylene polyamine in which the acyl radical has from 7 to 18 carbonatoms, an alkyl imidazoline having an alkyl radical having from 7 to 18carbon atoms, an allryl guanidlne having an alkyl radical having from 7to 18 carbon atoms, and from 0.02% to 0.05% of a mixed ether havingattached to the other oxygen a poly- 14 ethylene oudde radical and analiphatic hydrocarbon radical having from 7 to 18 carbon atoms.

8.- An article ofmanufacture according to claim 1v in which thecellulosic produit is insheet form.

4. The method of improving the spinning step in the production ofregenerated cellulose by the viscose process from raw cotton whichcomprises adding prior to the completion of shredding from 0.01% to 0.2%by weight, based on the bone dry weight of the cotton, of acation-active amino compound selected from the group consisting of analkyl amine having from 7 to 18 carbon atoms. an alkyl alkanolaminehaving at least one alkyl radical having froni- 8 to 14 carbon atoms andhaving from 14 to 18 total carbon atoms, a lauryl ether of analkanolamine, lauryl piperidine, lauryl methyl cyclohexylamine, anacylated polyethylene polyamine in which the acyl radical has from 7 to18 carbon atoms, an acylated hydroxyethyl polyethylene polyamine inwhich the acyl radical has from 7 to 18 carbon atoms. an alkylimidazoline having an alkyl radical having from 7 to 18 carbon atoms andan alkyl 'guanidine having an llavl radical having from 7 to 18 carbonatoms.

5. The method of improving the spinning-step in the production ofregenerated cellulose by the viscose process from raw cotton whichcomprises adding prior to the completion of shredding from 0.01% to 0.2%by weight, based on the bone dry weight of the cotton, of acation-active amine compound selected from the group of an alkyl aminehaving from 7 to 18 carbon atoms. an alkyl alkanolamine having at leastone alkyl radical having from 8 to 14 carbon atoms and having from 14 to18 total carbon atoms, a lauryl ether of an alkanolamine, laurylpiperldine, lauryl methyl cycloheiwlamine. an acylated polyethylenepolyamine in which the acyl radical has from 7 to 18 carbon atoms, anacylated hydroflethyl polyethylene polyamine in which the acyl radicalhas from 7 to 18 carbon atoms, an alkyl imidazoline having an alkylradical having from 7 to 18 carbon atoms, an allwl guanidine having analkyl radical having from 7 to 18 carbon atoms, and from0.02% to 0.05%of a mixed ether having attached to the ether oxygen a polyethyleneoxide radical and an aliphatic hydrocarbon radical having from 7 to 18carbon atoms.

PAUL HENRY KENNETH RUSSELL GRAY.

REFERENCES CITED 0 The following references are of record in the NumberName Date an 1,802,257 Jaeck Apr. 21, 1981 1,959,930 Schmidt et al. u---May 22, 1934 2,004,476 Bars June 11, 1935 2,125,031 Polak et al July 26,1928 2,168,280 Eustis ,Aug. 1, 1939 0! 2,182,306 Ulrich Dec. 5, 19392,236,617 Brandt Apr. 1, 1941 2,290,880 Katzman et al July 28, 19422,294,379 Bley Sept. 1, 1942 2,297,135 Davis Sept. 29, 1942 to 2,302,589Rose Nov. 17, 1942 2,310,207 Bley Feb. 9, 1943 2,310,208 Bley Feb. 9,1943 2,331,936 Schlosser et a]. nu. Oct. 19, 1948 2.393.817

8chlosseretai......-Jan.29.l940

Certificate of Correction Patent No. 2,481,692 September 13, 1949 PAULHENRY SCHLOSSER ET AL..

It is hereby certified that errors ap ieer in the printed specificationof the above numbered patent requiring correction as follows:

Column 4, line 46, for the word roaming readf'oa'ming; same line, forviscoees reed viscose; column 7, line 44, for from reedform; column 9,line 63, before coconu strike out a; column 10, line 5, for monemidereed monoamide; column 14, line 4, for -produit reed product; and thatthe said Letters Patent should be read withtheee corrections thereinthat the seine may conform to the record of the case-in the PatentOflice.

Signed and sealed this 14th day of February,-A. D. 1950.

THOMAS F. MURPHY,

Am'atmt Oonmiuioner-of-Batmta.

